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US5378817A - Reactive dyestuffs for dyeing and printing materials containing OH groups or amide groups - Google Patents

Reactive dyestuffs for dyeing and printing materials containing OH groups or amide groups Download PDF

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US5378817A
US5378817A US08/004,807 US480793A US5378817A US 5378817 A US5378817 A US 5378817A US 480793 A US480793 A US 480793A US 5378817 A US5378817 A US 5378817A
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radical
alkyl
alkoxy
dyestuff
red
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Konrad Bootz
Karl-Josef Herd
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/4401—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system

Definitions

  • the invention relates new reactive dyestuffs, their preparation and their use.
  • Reactive dyestuffs are already known from numerous publications, see DE-A 30 19 960 (U.S. Pat. No. 4,515,598), DE-A-19 22 940 (U.S. Pat. No. 3,718,641), EP-A-167 490, EP-A-133 843 (U.S. Pat. Nos. 4,746,732, 4,935,501, 4,996,304) and EP-A-40 806 (U.S. Pat. No. 4,649,193).
  • the present invention is based on the object of providing improved reactive dyestuffs.
  • FB the radical of a dyestuff preferably of the mono- or polyazo, metal complex azo, anthraquinone, phthalcyanine, formazan, azomethine, dioxaine, phenazine, stilbene, triphenyhethane, xanthene, thioxanthone, nitroaryl, naphthoquinone, pyrenquinone or perylenetetracarbide series,
  • B and B 1 identically or differently, a direct bond or a bridge member to a ring C atom of an aromatic-carbocyclic or to a ring C or N atom of an aromatic-heterocyclic ring in FB,
  • Z a heterocyclic fibre-reactive radical without a further chromophoric part
  • R and R 1 identically or differently, H or optionally substituted C 1 -C 6 -alkyl (preferred substituents: halogen, OH, COOH, SO 3 H and OSO 3 H).
  • Suitable bridge members B and B 1 are, for example, ##STR5## wherein the asterisk marks the linkage point with FB, R b and R bb independently of one another denote H or C 1 -C 6 -alkyl, which can be substituted, in particular by halogen, OH, COOH, SO 3 H or OSO 3 H,
  • Alk denotes straight-chain or branched C 1 -C 6 -alkylene which is optionally interrupted by hetero atoms or groupings containing hetero atoms, such as NR, O or S,
  • Ar denotes optionally substituted phenylene or naphthylene or a radical of a diphenyl or stilbene
  • Q denotes Alk, Ar or -Alk-Ar-, wherein Alk or Ar can contain further substituents, for example F, Cl, Br, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, carboxyl or sulpho and
  • L denotes F, Cl, Br, optionally substituted amino, OH, C 1 -C 4 -alkoxy, optionally substituted phenoxy or C 1 -C 4 -alkylthio.
  • Suitable fibre-reactive radicals Z are, in particular, those which contain at least one reactive substituent bonded to a 5- or 6-membered aromatic-heterocyclic ring, or to a monoazine, diazine or triazine ring, in particular a pyridine, pyrimidine, pyridazine, pyrazine, thiazine, oxazine or asymmetric or symmetric triazine ring, or to such a ring system which contains one or more fused-on aromatic-carbocyclic rings, or a quinoline, phthalazine, cinnoline, quinazoline, quinoxaline, acridine, phenazine or phenanthridine ring system, and which are not bonded to a further chromophore.
  • Examples which may be mentioned of the reactive substituents on the heterocyclic ring are halogen (Cl, Br or F), ammonium, including hydrazinium, pyridinium, picolinium, carboxypyridinium, sulphonium, sulphonyl, azido (N 3 ), thiocyanato, thiol-ether, oxyether, sulphinic acid and sulphonic acid.
  • halogen Cl, Br or F
  • ammonium including hydrazinium, pyridinium, picolinium, carboxypyridinium, sulphonium, sulphonyl, azido (N 3 ), thiocyanato, thiol-ether, oxyether, sulphinic acid and sulphonic acid.
  • alkyl radicals in particular monochloro and monofluorotriazinyl radicals which are substituted by alkyl, aryl, amino, monoalkylamino, dialkylamino, aralkylamino, arylamino, morpholino, piperidino, pyrrolidino, piperazino, alkoxy, aryloxy, alkylthio or arylthio, wherein alkyl preferably denotes optionally substituted C 1 -C 4 -alkyl, aralkyl preferably denotes optionally substituted phenyl-C 1 -C 4 -alkyl and aryl preferably denotes optionally substituted phenyl or naphthyl, and wherein preferred substituents for, alkyl are halogen, hydroxyl, cyan
  • 2-amino-4-fluoro-triazin-6-yl 2-methylamino-4-fluorotriazin-6-yl, 2-ethylamino-4-fluorotriazin-6-yl, 2-isopropylamino-4-fluoro-triazin-6-yl, 2-dimethylamino-4-fluorotriazin-6-yl, 2-diethylamino-4-fluoro-triazin-6-yl, 2- ⁇ -methoxy-ethylamino-4-fluoro-triazin-6-yl, 2- ⁇ -hydroxyethylamino-4-fluoro-triazin-6-yl, 2-di-( ⁇ -hydroxyethylamino)-4-fluoro-triazin-6-yl, 2- ⁇ -sulphoethylamino-4-fluoro-triazin-6-yl, 2- ⁇ -sulphoethylamino-methylamino-4-fluoro-triazin-6-yl
  • halogenotriazinyl radicals can also be linked to a second halogenotriazinyl radical or a halogenodiazinyl radical or one or more vinylsulphonyl or sulphatoethylsulphonyl radicals, or via a bridge member ##STR6## or in the case of the sulphatoethylsulphonyl or vinylsulphonyl group, via a bridge member ##STR7##
  • Mono-, di- or trihalogenopyrimidinyl radicals such as 2,4-dichloropyrimidin-6-yl-, 2,4,5-trichloropyrimidin-6-yl-, 2,4-dichloro-5-nitro- or -5-methyl- or -5-carboxymethyl- or -5-carboxy- or -5-cyano- or -5-vinyl- or -5-sulpho- or -5-mono-, -di- or -trichloromethyl- or -5-carbalkoxy-pyrimidin-6-yl-, 2,6-dichloropyrimidine-4-carbonyl-, 2,4-dichloropyrimidine-5-carbonyl-, 2-chloro-4-methyl-pyrimidine-5-carbonyl-, 2-methyl-4-chloropyrimidine-5-carbonyl-, 2-methylthio-4-fluoropyrimidine-5-carbonyl-, 6-methyl-2,4-dichloropyrimidine-5-carbonyl
  • Preferred reactive dyestuffs of the formula (1) are those wherein FB is the radical of a mono- or disazo dyestuff or of a metal complex azo dyestuff.
  • radicals --B--N(R)--X and --B 1 -N(R 1 )--Z are bonded to different or identical radicals of starting components, that is to say diazo and coupling components.
  • the radicals --B--N(R)--X and --B'--N(R')--Z are preferably bonded in each case to one component, that is to say diazo component or coupling component.
  • the reactive dyestuffs then have, for example, the formula ##STR9## wherein --K-- in formulae (1d) and (1e) represents the radical of a coupling component with two coupling points.
  • K the radical of a coupling component of the benzene, naphthalene, acetoacetic acid arylide or heterocyclic series; in the heterocyclic series, preferably a pyrazolone or pyridone radical.
  • radicals D, D 1 , D 2 and K can be substituted here by further azo groups or by radicals containing azo groups.
  • X, Z, B, B 1 , R and R 1 have the above-mentioned meanings.
  • D, D 1 and D 2 are, preferably, phenyl or phenylene which is optionally substituted by SO 3 H, chlorine, C 1 -C 4 -alkoxy, C 1 -C 4 -alkyl, carbalkoxy or sulphonamido, naphthyl or naphthylene which is optionally substituted by SO 3 H, chlorine, C 1 -C 4 -alkoxy or C 1 -C 4 -alkyl, 4-(phenylazo)phenyl which is optionally substituted by SO 3 H, and biphenylene which is optionally substituted by SO 3 H.
  • K represents, for example, the radical of a coupling component from the hydroxybenzene, hydroxynaphthalene, aminobenzene, aminonaphthalene or aminohydroxynaphthalene series, or represents a 5-hydroxy-3-methyl(or carboxy)pyrazolone a 6-hydroxy-2-pyridone or an acetoacetic acid arylide radical, optionally ring-substituted by C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy.
  • K can contain the customary constituents, in particular sulphonic acid groups.
  • Reactive dyestuffs which are furthermore possible are those of the formulae (1b) to (1f), wherein the radicals D, D 1 , D 2 and K can also contain a further reactive radical. This therefore also includes tri- and tetrafunctionally fibre-reactive dyestuffs.
  • the additional reactive radicals included in D or K can be bonded to D or K, like Z and X, via amino groups, or in another manner, for example by a direct bond.
  • the above explanations also apply in the general sense to the metal complexes of the mono- and disazo dyestuffs (1b -1f).
  • V a radical which can be eliminated under alkaline conditions, for example OSO 3 H, SSO 3 H, OCOCH 3 , OPO 3 H 2 , OSO 2 CH 3 , SCN, NHSO 2 CH 3 , Cl, Br, F, OCOC 6 H 5 , OSO 2 -C 6 H 4 , [N(CH 3 ) 3 ] + anion - or an optionally substituted pyridinium radical (substituents are, in particular, optionally substituted C 1 -C 4 -alkyl, COOH, SO 3 H, CN and carboxamide),
  • R 2 H, Cl, Br, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, CO 2 H or SO 3 H and
  • R 10 H or optionally substituted C 1 -C 6 -alkyl.
  • Preferred substituents of R 10 are halogen, OH, CO 2 H, SO 3 H and OSO 3 H.
  • Substituents in E are, for example: CH 3 , C 2 H 5 , CH 3 O, C 2 H 5 O, halogen or CO 2 H.
  • Particularly preferred reactive dyestuffs are those of the formula (2) wherein the benzene ring E is not further substituted, and reactive dyestuffs of the formula (3) wherein the benzene ring E is not further substituted.
  • Reactive dyestuffs which are furthermore preferred are those of the formula (4) ##STR15##
  • the reactive dyestuffs of the following formulae may be mentioned as further 10 useful representatives: ##STR16## wherein Pc represents a Cu or Ni phthalocyanine radical and the total number of substituents on the Pc skeleton is not more than 4; R and R 1 have the abovementioned meaning, and
  • T Cl, Br or OCH 3
  • Z, X, K and Alk have the abovementioned meanings
  • R 6 H, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, acylamino, in particular C 1 -C 4 -alkylcarbonylamino, C 1 -C 4 -alkylsulphonylamino, aminocarbonylamino, optionally substituted phenylcarbonylamino, Cl or Br,
  • R 7 H, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, OH or SO 3 H and
  • W an aliphatic bridge member, in particular C 2 -C 4 -alkylene.
  • the benzene rings E are preferably likewise not further substituted; diazo components which are used in this case are, above all, 1,3-phenylenediamine-4-sulphonic acid, 1,4-phenylenediamine-2-sulphonic acid, 1,4-phenylenediamine-2,5-disulphonic acid or 1,3-phenylenediamine-4,6-disulphonic acid.
  • the radical R in formulae (9) to (40) is, in particular, hydrogen, methyl or ethyl.
  • Preferred reactive dyestuffs are, above all, those of the formulae (2) to (40) wherein Z is an unsubstituted or substituted aminofluoro-s-triazine radical, and wherein --NR 4 R 5 preferably represents: --NH 2 , morpholino, N- ⁇ -hydroxyethylamino, N,N-di- ⁇ -hydroxyethylamino, ⁇ -sulphoethylamino, phenylamino, which is optionally substituted in the phenyl nucleus by chlorine, methyl, ethyl, methoxy, ethoxy, acetylamino, hydroxyl, carboxyl, sulphomethyl or sulpho, N-C 1-4 -alkyl-phenylamino, which is optionally substituted in the phenyl nucleus by chlorine, methyl or ethyl, N-(sulpho-C 1-4 -alkyl)-phenylamino, which is optional
  • Preferred dyestuffs (2) to (40) are those in which ##STR20##
  • One process for the preparation of the dyestuffs (1) comprises a procedure in which dyestuffs ##STR21## or the corresponding dyestuff precursors, are reacted with a reactive component ##STR22## and then with a reactive component
  • Hal Cl, Br or F
  • precursors in the case where precursors are used, these are then converted into the desired end dyestuffs, and if appropriate further modification reactions are then carried out.
  • the diazo components and the coupling components together must contain two amino groups --N(R)H and --N(R 1 )H, and if appropriate further acylatable amino groups. If appropriate, corresponding acetylamino or nitro compounds are used, in which case the acetylamino or nitro group is converted into the NH 2 group by hydrolysis or reduction before the condensation with a halogenotriazine, halogenopyrimidine or the like.
  • the reactive radicals X and Z are introduced by condensation of dyestuffs or dyestuff precursors which contain acylatable amino groups with fibre-reactive halogenated acylating agents.
  • the preparation of the end dyestuffs from precursors is usually by coupling reactions which lead to azo dyestuffs.
  • the reactions are carried out stepwise in succession, the sequence of the simple reactions between the individual reaction components advantageously depending on the particular conditions. Since hydrolysis of a halogenotriazine, (2-chloroethylsulphonyl-methyl)-benzoyl or halogenopyrimidine radical etc. occurs under certain conditions, an intermediate product which contains acetylamino groups must be hydrolysed for the purpose of splitting off the acetyl groups before it is subjected to condensation with an aminodifluorotriazine or trifluorotriazine and the like.
  • a further possible modification reaction is, for example, subsequent reaction of a dihalogenotriazinyl radical with an amine.
  • the reaction during preparation of a secondary condensation product of amine HNR 4 R 5 , 2,4,6-trihalogeno-s-triazine and diaminobenzenesulphonic acid which is advantageously carried out first, that of the trihalogenotriazine with the amine or with the diaminobenzenesulphonic acid, varies from case to case and depends above all on the solubility of the amino compounds participating and the basicity of the amino groups to be acylated. The most important process variants are described in the embodiment examples.
  • Suitable starting compounds for the preparation of mono-or polyazo dyestuffs (1) are, for example:
  • an aminoacetylamino compound from which the acetyl group is split off again subsequently by hydrolysis is to be used instead of a diamine as the diazo component, as is described above in the explanations of the process variants, the monoacetyl compounds of the abovementioned diazo components are possible, for example 1-acetylamino-3-aminobenzene-4-sulphonic acid or 1-acetylamino-4-aminobenzene-3-sulphonic acid.
  • diazo components which can also be used are those which contain no acylatable amino group in addition to the amino group to be diazotised, such as, for example, aminobenzene, 1-amino-2-, -3- or -4-methylbenzene, 1-amino-2-, -3- or -4-methoxybenzene, 1-amino-2-, -3- or -4-chlorobenzene, 1-amino-2,5-dichlorobenzene, 1-amino-2,5-dimethylbenzene, 1-amino-3-methyl-6-methoxybenzene, 1-amino-2-methoxy-4-nitrobenzene, 1-aminobiphenyl, 1-aminobenzene-2-, -3- or -4-carboxylic acid, 2-amino
  • 1-Amino-3-methylbenzene 1-amino-2-methoxy-5-methylbenzene, 1-amino-2,5-dimethylbenzene, 3-aminophenylurea, 1-amino-3-acetylaminobenzene, 1-amino-3-hydroxyacetylaminobenzene, 1,3-diaminobenzene-4-sulphonic acid, 1-aminonaphthalene-6- or -8-sulphonic acid, 1-amino-2-methoxynaphthalene-6-sulphonic acid, 2-aminonaphthalene-5,7-disulphonic acid, 1-amino-8-hydroxynaphthalene-6-sulphonic acid, 1-amino-8-hydroxynaphthalene-2,4-disulphonic acid, 2-hydroxy-3-aminonaphthalene-5,7-disulphonic acid, 1-amino-8-hydroxynaphthalene-2,4,6-trisulphonic acid, 1-hydroxy-8-acetylamin
  • the diazotisation of the diazo components or of the intermediate products containing a diazotisable amino group is as a rule carried out by the action of nitrous acid in aqueous-mineral acid solution at a low temperature.
  • the coupling to the coupling components is carried out at strongly acid, neutral to weakly alkaline pH values.
  • the condensation of the reactive components with the diazo components and the coupling components and with the amines or with acylatable monoazo or disazo intermediate products or with the dyestuffs containing amino groups is preferably carried out in aqueous solution or suspension, at a low temperature and at a weakly acid, neutral to weakly alkaline pH value.
  • the hydrogen halide liberated during the condensation is advantageously neutralised continuously by addition of aqueous alkali metal hydroxides, carbonates or bicarbonates.
  • the formulae shown are those of the free acids.
  • the salts in particular the alkali metal salts, such as sodium, potassium or lithium salts, are in general obtained during the preparation.
  • the charge resulting from quaternisation with pyridines is compensated by a counter-ion, for example chloride, fluoride or sulphate, depending on the isolation conditions; or the dyestuffs form inner salts with sulpho or carboxyl groups.
  • the dyestuffs can also be employed as concentrated solutions.
  • the dyestuffs according to the invention are outstandingly suitable for dyeing and printing naturally occurring and synthetic materials containing OH groups or amide groups, in particular those of cellulose and polyamides. They are particularly suitable for dyeing cellulose materials by the exhaustion and cold pad-batch process, and for printing cotton and viscose staple.
  • Dyeings having good general fastness properties, in particular wet fastness properties, are obtained, with a good build-up capacity and high fixing yields.
  • the temperature is increased to 50° C. 40 parts of calcined sodium carbonate and a further 60 parts of sodium chloride being added after 30 minutes.
  • the temperature is kept at 50° C. for 30 minutes, the fabric is rinsed and the dyeing is then soaped for 15 minutes in a 0.3% strength boiling solution of an ion-free detergent, rinsed and dried.
  • a) 0.2 mol of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid is dissolved in 350 ml of water at pH 6.5, and the solution is cooled to 0° C. with 350 g of ice.
  • 0.21 mol of 2,4,6-trifluoro-1,3,5-triazine (cyanuric fluoride) is added, and the pH is kept at between 3.5 and 4 with Na 2 CO 3 solution.
  • 0.2 mol of morpholine is added, and the pH is then brought to 7 with sodium carbonate solution. During this procedure, the temperature rises to about 10° C.
  • the mixture is subsequently stirred for 15 minutes, and the above diazotisation mixture a) is added dropwise in the course of 1 hour.
  • a pH of 5.5-6.5 is maintained with 1 molar sodium bicarbonate solution.
  • the dyestuff is salted out with NaCl, isolated and dried.
  • the dyestuff of the formula ##STR24## dyes cotton in red shades.
  • the dyestuffs of the following Examples 3-31 of the general formula ##STR25## can be prepared in an analogous manner using the diazo and coupling components and amines listed. They dye cotton in the colour shades listed.
  • X represents the following particular radicals: ##STR26##
  • 0.2 mol of 8-(4'-amino-benzoylamino)-1-naphthol-3,6-disulphonic acid is dissolved in 800 ml of water at a pH of 7 with sodium carbonate solution (20 g/100 ml). A pH of 4.5 is established with 10% strength CHl solution. 0.2 mol of 2,4,6-trifluoropyrimidine is added, and the mixture is heated up to 30° C. A pH of 4.5-6 is maintained with sodium carbonate solution (20 g/100 ml). The reaction has ended after 4 hours.
  • Examples 34-68 of the formula ##STR94## can be prepared as described in Example 32 or 33 if the corresponding intermediate products are employed. They dye cotton in the colour shades shown.
  • X is represented by X 1 to X 4 with the abovementioned meanings.
  • the dyestuff is salted out, isolated, dried and ground. It has the following formula ##STR167## and dyes cotton in red shades.
  • the mixture is subsequently stirred for 10 minutes.
  • the dyestuff is salted out with NaCl, isolated and dried.
  • the resulting dyestuff of the formula ##STR213## dyes cotton in red shades.
  • the dyestuffs of the following Examples 92-111 of the general formula ##STR214## are obtained by varying the diazo components, coupling components and amines. They dye cotton in the shades shown.
  • X 1 and X 3 have the abovementioned meaning.
  • the dyestuffs of Examples 126-131 of the general formula ##STR297## wherein X X 1 or X 3 , with the abovementioned meaning, can be prepared analogously, using the corresponding diazo and coupling components and amines. In some cases, it is more advantageous to carry out the condensation with cyanuric chloride and the amine at the end of the synthesis sequence.
  • a pH of 7-8 is maintained with sodium carbonate solution (20 g/100 ml). The temperature is 10°-15° C.
  • the dyestuff is salted out with NaCl, isolated and dried.
  • the resulting dyestuff of the formula ##STR313## dyes cotton in red shades.

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Abstract

Reactive dyestuffs of the formula ##STR1## wherein Z=a heterocyclic reactive group and the remaining groups have the meaning given in the description, are outstandingly suitable for dyeing and printing materials containing hydroxyl groups or amide groups.

Description

The invention relates new reactive dyestuffs, their preparation and their use.
Reactive dyestuffs are already known from numerous publications, see DE-A 30 19 960 (U.S. Pat. No. 4,515,598), DE-A-19 22 940 (U.S. Pat. No. 3,718,641), EP-A-167 490, EP-A-133 843 (U.S. Pat. Nos. 4,746,732, 4,935,501, 4,996,304) and EP-A-40 806 (U.S. Pat. No. 4,649,193).
The present invention is based on the object of providing improved reactive dyestuffs.
The invention relates to reactive dyestuffs of the formula ##STR2## in particular dyestuffs of the formula ##STR3## where X= ##STR4## FB=the radical of a dyestuff preferably of the mono- or polyazo, metal complex azo, anthraquinone, phthalcyanine, formazan, azomethine, dioxaine, phenazine, stilbene, triphenyhethane, xanthene, thioxanthone, nitroaryl, naphthoquinone, pyrenquinone or perylenetetracarbide series,
B and B1 =identically or differently, a direct bond or a bridge member to a ring C atom of an aromatic-carbocyclic or to a ring C or N atom of an aromatic-heterocyclic ring in FB,
M=CH═CH2 or CH2 CH2 --V, wherein
V=OH or a radical which can be eliminated under alkaline conditions, for example OSO3 H, SSO3 H, OCOCH3, OPO3 H2, OSO2 CH3, SCN, NHSO2 CH3, Cl, Br, F, OCOC6 H, OSO2 -C8 H4, [N(CH3)3 ]+ anion- or an optionally substituted pyridinium radical (substituents are, in particular, optionally substituted C1 -C4 -alkyl, COOH, SO3 H, CN or carboxamide), (anion=for example, Cl, HSO4, HCO3 and the like),
Z=a heterocyclic fibre-reactive radical without a further chromophoric part and
R and R1 =identically or differently, H or optionally substituted C1 -C6 -alkyl (preferred substituents: halogen, OH, COOH, SO3 H and OSO3 H).
Suitable bridge members B and B1 are, for example, ##STR5## wherein the asterisk marks the linkage point with FB, Rb and Rbb independently of one another denote H or C1 -C6 -alkyl, which can be substituted, in particular by halogen, OH, COOH, SO3 H or OSO3 H,
Alk denotes straight-chain or branched C1 -C6 -alkylene which is optionally interrupted by hetero atoms or groupings containing hetero atoms, such as NR, O or S,
Ar denotes optionally substituted phenylene or naphthylene or a radical of a diphenyl or stilbene,
Q denotes Alk, Ar or -Alk-Ar-, wherein Alk or Ar can contain further substituents, for example F, Cl, Br, C1 -C4 -alkyl, C1 -C4 -alkoxy, carboxyl or sulpho and
L denotes F, Cl, Br, optionally substituted amino, OH, C1 -C4 -alkoxy, optionally substituted phenoxy or C1 -C4 -alkylthio.
Suitable fibre-reactive radicals Z, i.e. those which react with the OH or NH groups of the fibres under dyeing conditions to form covalent bonds, are, in particular, those which contain at least one reactive substituent bonded to a 5- or 6-membered aromatic-heterocyclic ring, or to a monoazine, diazine or triazine ring, in particular a pyridine, pyrimidine, pyridazine, pyrazine, thiazine, oxazine or asymmetric or symmetric triazine ring, or to such a ring system which contains one or more fused-on aromatic-carbocyclic rings, or a quinoline, phthalazine, cinnoline, quinazoline, quinoxaline, acridine, phenazine or phenanthridine ring system, and which are not bonded to a further chromophore.
Examples which may be mentioned of the reactive substituents on the heterocyclic ring are halogen (Cl, Br or F), ammonium, including hydrazinium, pyridinium, picolinium, carboxypyridinium, sulphonium, sulphonyl, azido (N3), thiocyanato, thiol-ether, oxyether, sulphinic acid and sulphonic acid.
The following examples may be mentioned specifically:
2,4-difluorotriazin-6-yl, 2,4-dichlorotriazin-6-yl and monohalogeno-sym.-triazinyl radicals, in particular monochloro and monofluorotriazinyl radicals which are substituted by alkyl, aryl, amino, monoalkylamino, dialkylamino, aralkylamino, arylamino, morpholino, piperidino, pyrrolidino, piperazino, alkoxy, aryloxy, alkylthio or arylthio, wherein alkyl preferably denotes optionally substituted C1 -C4 -alkyl, aralkyl preferably denotes optionally substituted phenyl-C1 -C4 -alkyl and aryl preferably denotes optionally substituted phenyl or naphthyl, and wherein preferred substituents for, alkyl are halogen, hydroxyl, cyano, vinylsulphonyl, substituted alkylsulphonyl, dialkylamino, morpholino, C1 -C4 -alkoxy, vinylsulphonyl-C2 -C4 -alkoxy, substituted alkylsulphonyl-C2 -C4 -alkoxy, carboxyl, sulpho or sulphato, and preferred substituents for phenyl and naphthyl are sulpho, C1 -C4 -alkyl, C1 -C4 -alkoxy, carboxyl, halogen, acylamino, vinylsulphonyl, substituted alkylsulphonyl, hydroxyl and amino;
2-amino-4-fluoro-triazin-6-yl, 2-methylamino-4-fluorotriazin-6-yl, 2-ethylamino-4-fluorotriazin-6-yl, 2-isopropylamino-4-fluoro-triazin-6-yl, 2-dimethylamino-4-fluorotriazin-6-yl, 2-diethylamino-4-fluoro-triazin-6-yl, 2-β-methoxy-ethylamino-4-fluoro-triazin-6-yl, 2-β-hydroxyethylamino-4-fluoro-triazin-6-yl, 2-di-(β-hydroxyethylamino)-4-fluoro-triazin-6-yl, 2-β-sulphoethylamino-4-fluoro-triazin-6-yl, 2-β-sulphoethyl-methylamino-4-fluoro-triazin-6-yl, 2-carboxymethylamino-4-fluorotriazin-6-yl, 2-di-(carboxymethylamino)-4-fluoro-triazin-6-yl, 2-sulphomethyl-methylamino-4-fluoro-triazin-6-yl, 2-β-cyanoethylamino-4-fluoro-triazin-6-yl, 2-benzylamino-4-fluoro-triazin-6-yl, 2-β-phenylethylamino-4-fluorotriazin-6-yl, 2-benzyl-methylamino-4-fluoro-triazin-6-yl, 2-(4'-sulphobenzyl)-amino-4-fluoro-triazin-6-yl, 2-cyclohexylamino-4-fluoro-triazin-6-yl, 2-(o-, m- or p-methylphenyl)-amino-4-fluoro-triazin-6-yl, 2-(o-, m- or p-sulphophenyl)-amino-4-fluoro-triazin-6-yl, 2-(2', 5'-disulphophenyl)-amino-4-fluoro-triazin-6-yl, 2-(o-, m- or p-chlorophenyl)-amino-4-fluoro-triazin-6-yl, 2-o-, m- or p-methoxyphenyl)-amino-4-fluoro-triazin-6-yl, 2-(2'-methyl-4'-sulphophenyl)-amino-4-fluoro-triazin-6-yl, 2-(2'-methyl-5'-sulphophenyl)-amino-4-fluoro-triazin-6-yl, 2-(2'-chloro-4'-sulphophenyl)-amino-4-fluoro-triazin-6-yl, 2-(2'-chloro-5'-sulphophenyl)-amino-4-fluoro-triazin-6-yl, 2-( 2'-methoxy-4'-sulphophenyl)-amino-4-fluoro-triazin6-yl, 2-(o-, m- or p-carboxyphenyl)-amino-4-fluoro-triazin-6-yl, 2-(2',4'-disulphophenyl)-amino-4-fluoro-triazin-6-yl, 2-(3',5'-disulphophenyl)-amino-4-fluoro-triazin-6-yl, 2-(2'-carboxy-4'-sulphophenyl)-amino-4-fluoro-triazin-6-yl, 2-(2'-carboxy-5'-sulphophenyl)-amino-4-fluoro-triazin-6-yl, 2-(6'-sulphonaphth-2'-yl)-amino-4-fluoro-triazin-6-yl, 2-(4',8'-disulphonaphth-2'-yl)-amino-4-fluoro-triazin-6-yl, 2-(6',8'-disulphonaphth-2'-yl)-amino-4-fluoro-triazin-6-yl, 2-(N-methyl-N-phenyl)-amino-4-fluoro-triazin-6-yl, 2-(N-ethyl-N-phenyl)-amino-4-fluoro-triazin-6-yl, 2-(N-β-hydroxyethyl-N-phenyl)-amino-4-fluoro-triazin-6-yl, 2-(N-isopropyl-N-phenyl)-amino-4-fluoro-triazin-6-yl, 2-morpholino-4-fluoro-triazin-6-yl, 2-piperidino-4-fluoro-triazin-6-yl, 2-(4',6',8'-trisulphonaphth-2'-yl)-amino-4-fluoro-triazin-6-yl, 2-(3',6',8'-trisulphonaphth-2'-yl)-amino-4-fluoro-triazin-6-yl, 2-(3',6'-disulphonaphth-1'-yl)-amino-4-fluoro-triazin-6-yl, N-methyl-N-(2,4-dichlorotriazin-6-yl)-carbamyl, N-methyl-N-(2-methylamino-4-chlorotriazin-6-yl)-carbamyl, N-methyl-N-(2-dimethylamino-4-chlorotriazin-6-yl)-carbamyl, N-methyl-or N-ethyl-N-(2,4-dichlorotriazin-6-yl)-aminoacetyl, 2-methoxy-4-fluoro-triazin-6-yl, 2-ethoxy-4-fluoro-triazin-6-yl, 2-phenoxy-4-fluoro-triazin-6-yl, 2-(o-, m- or p-sulphophenoxy)-4-fluoro-triazin-6-yl, 2-(o-, m- or p-methyl- or -methoxy-phenoxy)-4-fluoro-triazin-6-yl, 2-β-hydroxyethylmercapto-4-fluoro-triazin-6-yl, 2-phenylmercapto-4-fluoro-triazin-6-yl, 2-(4'-methylphenyl)mercapto-4-fluorotriazin-6-yl, 2-(2',4'-dinitrophenyl)mercapto-4-fluoro-triazin-6-yl, 2-methyl-4-fluoro-triazin-6-yl, 2-phenyl-4-fluoro-triazin-6-yl and the corresponding 4-chloro- and 4-bromo-triazinyl radicals, and the corresponding radicals obtainable by halogen exchange with tertiary bases, such as trimethylamine, triethylamine, dimethyl-β-hydroxyethylamine, triethanolamine, N,N-dimethylhydrazine, pyridine, α-, β- or γ-picoline, nicotinic acid or isonicotinic acid, sulphinates, in particular benzenesulphinic acid, or hydrogen sulphite.
The halogenotriazinyl radicals can also be linked to a second halogenotriazinyl radical or a halogenodiazinyl radical or one or more vinylsulphonyl or sulphatoethylsulphonyl radicals, or via a bridge member ##STR6## or in the case of the sulphatoethylsulphonyl or vinylsulphonyl group, via a bridge member ##STR7##
Examples of radicals linked in this way are: ##STR8##
Mono-, di- or trihalogenopyrimidinyl radicals, such as 2,4-dichloropyrimidin-6-yl-, 2,4,5-trichloropyrimidin-6-yl-, 2,4-dichloro-5-nitro- or -5-methyl- or -5-carboxymethyl- or -5-carboxy- or -5-cyano- or -5-vinyl- or -5-sulpho- or -5-mono-, -di- or -trichloromethyl- or -5-carbalkoxy-pyrimidin-6-yl-, 2,6-dichloropyrimidine-4-carbonyl-, 2,4-dichloropyrimidine-5-carbonyl-, 2-chloro-4-methyl-pyrimidine-5-carbonyl-, 2-methyl-4-chloropyrimidine-5-carbonyl-, 2-methylthio-4-fluoropyrimidine-5-carbonyl-, 6-methyl-2,4-dichloropyrimidine-5-carbonyl-, 2,4,6-trichloropyrimidine-5-carbonyl-, 2,4-dichloropyrimidine-5-sulphonyl-, 2-chloro-quinoxaline-3-carbonyl-, 2- or 3-monochloroquinoxaline-6-carbonyl-, 2- or 3-monochloroquinoxaline-6-sulphonyl-,2,3-dichloroquinoxaline-5- or -6-carbonyl-, 2,3-dichloroquinoxaline-5- or -6-sulphonyl-, 1,4-dichlorophthalazine-6-sulphonyl-or -6-carbonyl-, 2,4-dichloroquinazoline-7- or -6-sulphonyl- or -carbonyl-, 2- or 3- or 4-(4',5'-dichloropyridaz-6'-on-1'-yl)-phenylsulphonyl- or -carbonyl-, β-(4',5'-dichloropyridaz-6'-on-1'-yl)ethylcarbonyl, N-methyl-N-(2,3-dichloroquinoxaline-6-sulphonyl)-aminoacetyl-, N-methyl-N-(2,3-dichloroquinoxaline-6-carbonyl)-aminoacetyl- and the corresponding bromine and fluorine derivatives of the above-mentioned chlorine-substituted heterocyclic radicals, and amongst these, for example, 2-fluoro-4-pyrimidinyl-, 2,6-difluoro-4-pyrimidinyl-, 2,6-difluoro-5-chloro-4-pyrimidinyl-, 2-fluoro-5,6-dichloro-4-pyrimidinyl-, 2,6-difluoro-5-methyl-4-pyrimidinyl-, 2-fluoro-5-methyl-6-chloro-4-pyrimidinyl-, 2-fluoro-5-nitro-6-chloro-4-pyrimidinyl-, 5-bromo-2-fluoro-4-pyrimidinyl-, 2-fluoro-5-cyano-4-pyrimidinyl-, 2-fluoro-5-methyl-4-pyrimidinyl-, 2,5,6-trifluoro-4-pyrimidinyl-, 5-chloro-6-chloromethyl-2-fluoro-4-pyrimidinyl-, 5-chloro-6-dichloromethyl-2-fluoro-4-pyrimidinyl-, 5-chloro-6-trichloromethyl-2-fluoro-4-pyrimidinyl-, 5-chloro-2-chloromethyl-6-fluoro-4-pyrimidinyl-, 5-chloro-2-dichloromethyl-6-fluoro-4-pyrimidinyl-, 5-chloro-2-trichloromethyl-6-fluoro-4-pyrimidinyl-, 5-chloro-2-fluorodichloromethyl-6-fluoro-4-pyrimidinyl-, 2,6-difluoro-5-bromo-4-pyrimidinyl-, 2-fluoro-5-bromo-6-methyl-4-pyrimidinyl-, 2-fluoro- 5-bromo6-chloromethyl-4-pyrimidinyl-, 2,6-difluoro-5-chloromethyl-4-pyrimidinyl-, 2,6-difluoro-5-nitro-4-pyrimidinyl-, 2-fluoro-6-methyl-4-pyrimidinyl-, 2-fluoro-5-chloro-6-methyl-4-pyrimidinyl-, 2-fluoro-5-chloro-4-pyrimidinyl-, 2-fluoro-6-chloro-4-pyrimidinyl-, 6-trifluoromethyl-5-chloro-2-fluoro-4-pyrimidinyl-, 6-trifluoromethyl-2-fluoro-4-pyrimidinyl-, 2-fluoro-5-nitro-4-pyrimidinyl-, 2-fluoro-5-trifluoromethyl-4-pyrimidinyl-, 2-fluoro-5-phenyl- or -5-methylsulphonyl-4-pyrimidinyl-, 2-fluoro-5-carboxamido-4-pyrimidinyl-, 2-fluoro-5-carbomethoxy-4-pyrimidinyl-, 2-fluoro-5-bromo-6-trifluoromethyl-4-pyrimidinyl-, 2-fluoro-6-carboxamido-4-pyrimidinyl-, 2-fluoro-6-carbomethoxy-4-pyrimidinyl-, 2-fluoro-6-phenyl-4-pyrimidinyl-, 2-fluoro-6-cyano-4-pyrimidinyl-, 5-chloro-6-fluoro-2-methyl-4-pyrimidinyl-, 5,6-difluoro-2-trifluoromethyl-4-pyrimidinyl-, 5-chloro-6-fluoro-2-dichlorofluoromethyl-4-pyrimidinyl-, 2-fluoro-5-chloropyrimidin-4-yl-, 2-methyl-4-fluoro-5-methylsulphonylpyrimidin-6-yl-, 2,6-difluoro-5-methylsulphonyl-4-pyrimidinyl-, 2,6-dichloro-5-methylsulphonyl-4-pyrimidinyl-, 2-fluoro-5-sulphonamido-4-pyrimidinyl-, 2-fluoro-5-chloro-6-carbomethoxy-4-pyrimidinyl- and 2,6-difluoro-5-trifluoromethyl-4-pyrimidinyl-; triazine radicals containing sulphonyl groups, such as 2,4-bis-(phenylsulphonyl)-triazin-6-yl-, 2-(3'-carboxyphenyl)sulphonyl-4-chlorotriazin-6-yl-, 2-(3'-sulphophenyl)sulphonyl-4-chlorotriazin-6-yl- and 2,4-bis-(3'-carboxyphenylsulphonyl)-triazin-6-yl-; pyrimidine rings containing sulphonyl groups, such as 2-carboxymethylsulphonylpyrimidin- 4-yl-, 2-methylsulphonyl-6-methyl-pyrimidin-4- yl-,2-methylsulphonyl-6-ethyl-pyrimidin-4-yl-, 2-phenylsulphonyl-5-chloro-6-methyl-pyrimidin-4-yl-, 2,6-bis-methylsulphonyl-pyrimidin-4-yl-, 2,6-bis-methylsulphonyl-5-chloro-pyrimidin-4-yl-, 2,4-bis-methylsulphonyl-pyrimidine-5-sulphonyl-, 2-methylsulphonyl-pyrimidin-4-yl-, 2-phenylsulphonyl-pyrimidin-4-yl-, 2-trichloromethyl-sulphonyl-6-methyl-pyrimidin-4-yl-, 2-methyl-sulphonyl-5-chloro-6-methyl-pyrimidin-4-yl-, 2-methylsulphonyl-5-bromo-6-methyl-pyrimidin-4-yl-, 2-methylsulphonyl-5-chloro-6-ethyl-pyrimidin-4-yl-, 2-methylsulphonyl-5-chloro-6-chloromethyl-pyrimidin-4-yl-, 2-methylsulphonyl-4-chloro-6-methylpyrimidine-5-sulphonyl-, 2-methylsulphonyl-5-nitro-6-methylpyrimidin-4-yl-, 2,5,6-trismethylsulphonyl-pyrimidin-4-yl-, 2-methylsulphonyl-5,6-dimethyl-pyrimidin-4-yl-, 2-ethylsulphonyl-5-chloro-6-methyl-pyrimidin-4-yl-, 2-methylsulphonyl-6-chloropyrimidin-4-yl-, 2,6-bis-methylsulphonyl-5-chloro-pyrimidin-4-yl-, 2-methylsulphonyl-6-carboxypyrimidin-4-yl-, 2-methylsulphonyl-5-sulpho-pyrimidin-4-yl-, 2-methylsulphonyl-6-carbomethoxy-pyrimidin-4-yl-, 2-methylsulphonyl-5-carboxy-pyrimidin-4-yl-, 2-methylsulphonyl-5-cyano-6-methoxy-pyrimidin-4-yl-, 2-methylsulphonyl-5-chloro-pyrimidin-4-yl-, 2-β-sulphoethylsulphonyl-6-methylpyrimidin-4-yl-, 2-methylsulphonyl-5-bromo-pyrimidin-4-yl-, 2-phenylsulphonyl-5-chloro-pyrimidin-4-yl-, 2-carboxymethylsulphonyl-5-chloro-6-methyl-pyrimidin-4-yl-, 2-methylsulphonyl-6-chloropyrimidine-4- or -5-carbonyl, 2,6-bis-(methylsulphonyl)-pyrimidine-4- or -5-carbonyl, 2-ethylsulphonyl-6-chloropyrimidine-5-carbonyl-, 2,4-bis-(methylsulphonyl)-pyrimidine-5-sulphonyl- and 2-methylsulphonyl-4-chloro-6-methylpyrimidine-5-sulphonyl- or -carbonyl-; 2-chlorobenzothiazole-5- or -6-carbonyl- or -5- or -6-sulphonyl-, 2-arylsulphonyl- or -alkylsulphonyl-benzothiazole-5- or -6-carbonyl- or -5- or -6-sulphonyl-, such as 2-methylsulphonyl- or 2-ethylsulphonyl-benzothiazole-5- or -6-sulphonyl- or -carbonyl-, 2-phenylsulphonylbenzothiazole-5- or -6-sulphonyl- or -carbonyl- and the corresponding 2-sulphonylbenzothiazole-5- or -6-carbonyl or -sulphonyl derivatives containing sulpho groups in the fused-on benzene ring, 2-chlorobenzoxazole-5- or -6-carbonyl- or -sulphonyl-, 2-chlorobenzimidazole-5- or -6-carbonyl- or -sulphonyl, 2-chloro-1-methylbenzimidazole-5- or -6-carbonyl- or -sulphonyl-, 2-chloro-4-methyl-1,3-thiazole-5-carbonyl- or -4- or -5-sulphonyl- and the N-oxide of 4-chloro- or 4-nitroquinoline-5-carbonyl.
Preferred reactive dyestuffs of the formula (1) are those wherein FB is the radical of a mono- or disazo dyestuff or of a metal complex azo dyestuff.
In this case, the radicals --B--N(R)--X and --B1 -N(R1)--Z are bonded to different or identical radicals of starting components, that is to say diazo and coupling components. The radicals --B--N(R)--X and --B'--N(R')--Z are preferably bonded in each case to one component, that is to say diazo component or coupling component. The reactive dyestuffs then have, for example, the formula ##STR9## wherein --K-- in formulae (1d) and (1e) represents the radical of a coupling component with two coupling points.
If the two radicals --B--N(R)--X and --B1 --N(R1)--Z are bonded to the same radical of a starting component D or K, this is, in particular, the radical of the coupling component K. The reactive dyestuffs then correspond to the formula ##STR10## wherein D, D1 and D2 =the radical of a diazo component of the benzene or naphthalene series and
K=the radical of a coupling component of the benzene, naphthalene, acetoacetic acid arylide or heterocyclic series; in the heterocyclic series, preferably a pyrazolone or pyridone radical.
The radicals D, D1, D2 and K can be substituted here by further azo groups or by radicals containing azo groups. X, Z, B, B1, R and R1 have the above-mentioned meanings.
Examples of D, D1 and D2 are, preferably, phenyl or phenylene which is optionally substituted by SO3 H, chlorine, C1 -C4 -alkoxy, C1 -C4 -alkyl, carbalkoxy or sulphonamido, naphthyl or naphthylene which is optionally substituted by SO3 H, chlorine, C1 -C4 -alkoxy or C1 -C4 -alkyl, 4-(phenylazo)phenyl which is optionally substituted by SO3 H, and biphenylene which is optionally substituted by SO3 H.
K represents, for example, the radical of a coupling component from the hydroxybenzene, hydroxynaphthalene, aminobenzene, aminonaphthalene or aminohydroxynaphthalene series, or represents a 5-hydroxy-3-methyl(or carboxy)pyrazolone a 6-hydroxy-2-pyridone or an acetoacetic acid arylide radical, optionally ring-substituted by C1 -C4 -alkyl or C1 -C4 -alkoxy.
K can contain the customary constituents, in particular sulphonic acid groups.
Reactive dyestuffs which are furthermore possible are those of the formulae (1b) to (1f), wherein the radicals D, D1, D2 and K can also contain a further reactive radical. This therefore also includes tri- and tetrafunctionally fibre-reactive dyestuffs.
The additional reactive radicals included in D or K can be bonded to D or K, like Z and X, via amino groups, or in another manner, for example by a direct bond. The above explanations also apply in the general sense to the metal complexes of the mono- and disazo dyestuffs (1b -1f).
Particularly preferred reactive dyestuffs according to the invention are those of the formula (1) or (1a)-(1f) wherein Z is a fibre-reactive fluorine-containing 4-pyrimidyl radical or a radical of the formula ##STR11## wherein R4 and R5 independently of one another are hydrogen, C1-4 -alkyl, which is optionally substituted by halogen, cyano, C1-4 -alkoxy, hydroxyl, carboxyl, sulpho or sulphato, benzyl, phenethyl, cyclohexyl, phenyl or --NHCH2 CH2 OCH2 CH2 --SO2 M (M=--CH═CH2 or --CH2 CH2 --V, where V=a radical which can be eliminated under alkaline conditions), phenyl, which is optionally substituted by halogen, nitro, cyano, trifluoromethyl, sulphamoyl, carbamoyl, C1-4 -alkyl, C1-4 -alkoxy, C1-4 -alkanoylamino, benzoylamino, ureido, hydroxyl, carboxyl, sulphomethyl or sulpho, or naphthyl, which is optionally substituted by halogen, nitro, C1-4 -alkoxy, C1-4 -alkanoylamino, hydroxyl, carboxyl or sulpho, or wherein R4 and R5 together with the amino nitrogen atom, form a morpholino, piperidino or piperazino radical, and wherein Y is Cl, F or an optionally substituted pyridinium radical.
Dyestuffs of the formula (1) which are furthermore preferred are those in which Z represents ##STR12## wherein Y=Cl, F or an optionally substituted pyridinium radical,
M=CH═CH2 or CH2 CH2 --V, wherein
V=a radical which can be eliminated under alkaline conditions, for example OSO3 H, SSO3 H, OCOCH3, OPO3 H2, OSO2 CH3, SCN, NHSO2 CH3, Cl, Br, F, OCOC6 H5, OSO2 -C6 H4, [N(CH3)3 ]+ anion- or an optionally substituted pyridinium radical (substituents are, in particular, optionally substituted C1 -C4 -alkyl, COOH, SO3 H, CN and carboxamide),
R2 =H, Cl, Br, C1 -C4 -alkyl, C1 -C4 -alkoxy, CO2 H or SO3 H and
R10 =H or optionally substituted C1 -C6 -alkyl.
Preferred substituents of R10 are halogen, OH, CO2 H, SO3 H and OSO3 H.
Preferred reactive dyestuffs are those of the formula (2) ##STR13## and of the formula (3) ##STR14## wherein R3 =hydrogen, methyl or ethyl, and the benzene ring E is optionally further substituted.
Substituents in E are, for example: CH3, C2 H5, CH3 O, C2 H5 O, halogen or CO2 H.
Particularly preferred reactive dyestuffs are those of the formula (2) wherein the benzene ring E is not further substituted, and reactive dyestuffs of the formula (3) wherein the benzene ring E is not further substituted.
Reactive dyestuffs which are furthermore preferred are those of the formula (4) ##STR15##
In addition to the reactive dyestuffs of the formulae (2), (3) and (4) described above, the reactive dyestuffs of the following formulae may be mentioned as further 10 useful representatives: ##STR16## wherein Pc represents a Cu or Ni phthalocyanine radical and the total number of substituents on the Pc skeleton is not more than 4; R and R1 have the abovementioned meaning, and
wherein T=Cl, Br or OCH3, and Z, X, K and Alk have the abovementioned meanings,
R6 =H, C1 -C4 -alkyl, C1 -C4 -alkoxy, acylamino, in particular C1 -C4 -alkylcarbonylamino, C1 -C4 -alkylsulphonylamino, aminocarbonylamino, optionally substituted phenylcarbonylamino, Cl or Br,
R7 =H, C1 -C4 -alkyl, C1 -C4 -alkoxy, OH or SO3 H and
W=an aliphatic bridge member, in particular C2 -C4 -alkylene.
In the preferred reactive dyestuffs of the formulae (5), (6), (9), (10), (11) and (30), the benzene rings E are preferably likewise not further substituted; diazo components which are used in this case are, above all, 1,3-phenylenediamine-4-sulphonic acid, 1,4-phenylenediamine-2-sulphonic acid, 1,4-phenylenediamine-2,5-disulphonic acid or 1,3-phenylenediamine-4,6-disulphonic acid. The radical R in formulae (9) to (40) is, in particular, hydrogen, methyl or ethyl.
In a preferred embodiment, ##STR17## where M=vinyl or CH2 CH2 Cl.
Preferred reactive dyestuffs are, above all, those of the formulae (2) to (40) wherein Z is an unsubstituted or substituted aminofluoro-s-triazine radical, and wherein --NR4 R5 preferably represents: --NH2, morpholino, N-β-hydroxyethylamino, N,N-di-β-hydroxyethylamino, β-sulphoethylamino, phenylamino, which is optionally substituted in the phenyl nucleus by chlorine, methyl, ethyl, methoxy, ethoxy, acetylamino, hydroxyl, carboxyl, sulphomethyl or sulpho, N-C1-4 -alkyl-phenylamino, which is optionally substituted in the phenyl nucleus by chlorine, methyl or ethyl, N-(sulpho-C1-4 -alkyl)-phenylamino, which is optionally substituted in the phenyl nucleus by chlorine, methyl or ethyl, N-(hydroxy-C1-4 -alkyl)phenylamino amino or sulphonaphthylamino, and the second reactive radical X represents the (2-chloroethylsulphonyl-methyl)benzoyl radical, such as, for example, dyestuffs of the formula (41) ##STR18##
Preferred reactive dyestuffs are those of the formula (42), wherein Z is a fibre-reactive halogen-containing pyrimidyl radical, for example ##STR19## where R=H, CH3 or C2 H5. Preferred dyestuffs (2) to (40) are those in which ##STR20##
One process for the preparation of the dyestuffs (1) comprises a procedure in which dyestuffs ##STR21## or the corresponding dyestuff precursors, are reacted with a reactive component ##STR22## and then with a reactive component
Z--Hal                                                     (VI)
wherein Hal=Cl, Br or F, and in the case where precursors are used, these are then converted into the desired end dyestuffs, and if appropriate further modification reactions are then carried out.
In the preparation of the preferred azo dyestuffs, the diazo components and the coupling components together must contain two amino groups --N(R)H and --N(R1)H, and if appropriate further acylatable amino groups. If appropriate, corresponding acetylamino or nitro compounds are used, in which case the acetylamino or nitro group is converted into the NH2 group by hydrolysis or reduction before the condensation with a halogenotriazine, halogenopyrimidine or the like. The reactive radicals X and Z are introduced by condensation of dyestuffs or dyestuff precursors which contain acylatable amino groups with fibre-reactive halogenated acylating agents. The preparation of the end dyestuffs from precursors is usually by coupling reactions which lead to azo dyestuffs.
Since the individual process steps mentioned above can be carried out in different sequences, various process variants are possible. In general, the reactions are carried out stepwise in succession, the sequence of the simple reactions between the individual reaction components advantageously depending on the particular conditions. Since hydrolysis of a halogenotriazine, (2-chloroethylsulphonyl-methyl)-benzoyl or halogenopyrimidine radical etc. occurs under certain conditions, an intermediate product which contains acetylamino groups must be hydrolysed for the purpose of splitting off the acetyl groups before it is subjected to condensation with an aminodifluorotriazine or trifluorotriazine and the like. A further possible modification reaction is, for example, subsequent reaction of a dihalogenotriazinyl radical with an amine. The reaction during preparation of a secondary condensation product of amine HNR4 R5, 2,4,6-trihalogeno-s-triazine and diaminobenzenesulphonic acid which is advantageously carried out first, that of the trihalogenotriazine with the amine or with the diaminobenzenesulphonic acid, varies from case to case and depends above all on the solubility of the amino compounds participating and the basicity of the amino groups to be acylated. The most important process variants are described in the embodiment examples.
Suitable starting compounds for the preparation of mono-or polyazo dyestuffs (1) are, for example:
Diazo components (D, D1 and D2)
1,3-Diaminobenzene, 1,4-diaminobenzene, 1,3-diamino-4-chlorobenzene, 1,3-diamino-4-methylbenzene, 1,3-diamino-4-ethylbenzene, 1,3-diamino-4-methoxybenzene, 1,3-diamino-4-ethoxybenzene, 1,4-diamino-2-methylbenzene, 1,4-diamino-2-methoxybenzene, 1,4-diamino-2-ethoxybenzene, 1,4-diamino-2-chlorobenzene, 1,4-diamino-2,5-dimethylbenzene, 1,4-diamino-2,5-diethylbenzene, 1,4-diamino-2-methyl-5-methoxybenzene, 1,4-diamino-2,5-dimethoxybenzene, 1,4-diamino-2,5-diethoxybenzene, 2,6-diaminonaphthalene, 1,3-diamino-2,4,6-trimethylbenzene, 1,4-diamino-2,3,5,6-tetramethylbenzene, 1,3-diamino-4-nitrobenzene, 4,4'-diaminostilbene, 4,4'-diaminodiphenylmethane, 4,4'-diaminobiphenyl(benzidine), 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 3,3'-dichlorobenzidine, 3,3'-dicarboxybenzidine, 3,3'-dicarboxymethoxy-benzidine, 2,2'-dimethylbenzidine, 4,2'-diaminodiphenyl (diphenyline), 2,6-diaminonaphthalene-4,8disulphonic acid, 1,4-diaminobenzene-2-sulphonic acid, 1,4-diaminobenzene-2,5-disulphonic acid, 1,4-diaminobenzene-2,6-disulphonic acid, 1,3-diaminobenzene-4-sulphonic acid, 1,3-diaminobenzene-4,6-disulphonic acid, 1,4-diamino-2-chlorobenzene-5-sulphonic acid, 1,4-diamino-2-methylbenzene-5-sulphonic acid, 1,5-diamino-6-methylbenzene-3-sulphonic acid, 1,3-diamino-6-methylbenzene-4-sulphonic acid, 3-(3'- or 4'-aminobenzoylamino)-1-aminobenzene-6-sulphonic acid, 1-(4'-aminobenzoylamino)-4-aminobenzene-2,5-disulphonic acid, 1,4-diaminobenzene-2-carboxylic acid, 1,3-diaminobenzene-4-carboxylic acid, 1,2-diaminobenzene-4-carboxylic acid, 1,3-diaminobenzene-5-carboxylic acid, 1,4-diamino-2-methylbenzene, 4,4'-diaminodiphenyl oxide, 4,4'-diaminodiphenylurea-2,2'-disulphonic acid, 4,4'-diaminodiphenyloxyethane-2,2'-disulphonic acid, 4,4' -diaminostilbene-2,2'-disulphonic acid, 4,4'-diaminodiphenylethane-2,2'-disulphonic acid, 2-amino-5-aminomethylnaphthalene-1-sulphonic acid, 2-amino-5-aminomethylnaphthalene-1,7-disulphonic acid and 1-amino-4-methoxy-5-aminomethylbenzene-6-sulphonic acid.
If an aminoacetylamino compound from which the acetyl group is split off again subsequently by hydrolysis is to be used instead of a diamine as the diazo component, as is described above in the explanations of the process variants, the monoacetyl compounds of the abovementioned diazo components are possible, for example 1-acetylamino-3-aminobenzene-4-sulphonic acid or 1-acetylamino-4-aminobenzene-3-sulphonic acid.
If the two radicals --B--N(R)--X and --B1 --N(R1)--Z in formula (1) are bonded to the same component, for example the coupling component, as is described above, diazo components which can also be used are those which contain no acylatable amino group in addition to the amino group to be diazotised, such as, for example, aminobenzene, 1-amino-2-, -3- or -4-methylbenzene, 1-amino-2-, -3- or -4-methoxybenzene, 1-amino-2-, -3- or -4-chlorobenzene, 1-amino-2,5-dichlorobenzene, 1-amino-2,5-dimethylbenzene, 1-amino-3-methyl-6-methoxybenzene, 1-amino-2-methoxy-4-nitrobenzene, 1-aminobiphenyl, 1-aminobenzene-2-, -3- or -4-carboxylic acid, 2-aminodiphenyl ether, 1-aminobenzene-2-, -3- or -4-sulphonamide, 1-aminobenzene-2-, -3- or -4-sulphonic acid, 1-aminobenzene-2,4- and -2,5-disulphonic acid, 1-amino-4-methylbenzene-2-sulphonic acid, 1-amino-3-methylbenzene-6-sulphonic acid, 1 -amino-6-methylbenzene-3- or -4-sulphonic acid, 1-aminonaphthalene, 2-aminonaphthalene, 1-aminonaphthalene-2-, -4-, -5-, -6-, -7- or -8-sulphonic acid, 2-aminonaphthalene-1-, -3-, -4-, -5-, -6-, -7- or -8-sulphonic acid, 1-aminonaphthalene-3,6- or -5,7-disulphonic acid, 2-aminonaphthalene-1,5-, -1,7-, -3,6-, -5,7-, -4,8- or -6,8-disulphonic acid, 1-aminonaphthalene-2,5,7-trisulphonic acid, 2-aminonaphthalene-1,5,7-, -3,6,8- or -4,6,8-trisulphonic acid, 4-aminoazobenzene-3,4'-disulphonic acid, 3-methoxy-4-amino-6-methylazobenzene-2',4'-disulphonic acid or 3-methoxy-4-amino-6-methylazobenzene-2',5'-disulphonic acid
Coupling components (K)
1-Amino-3-methylbenzene, 1-amino-2-methoxy-5-methylbenzene, 1-amino-2,5-dimethylbenzene, 3-aminophenylurea, 1-amino-3-acetylaminobenzene, 1-amino-3-hydroxyacetylaminobenzene, 1,3-diaminobenzene-4-sulphonic acid, 1-aminonaphthalene-6- or -8-sulphonic acid, 1-amino-2-methoxynaphthalene-6-sulphonic acid, 2-aminonaphthalene-5,7-disulphonic acid, 1-amino-8-hydroxynaphthalene-6-sulphonic acid, 1-amino-8-hydroxynaphthalene-2,4-disulphonic acid, 2-hydroxy-3-aminonaphthalene-5,7-disulphonic acid, 1-amino-8-hydroxynaphthalene-2,4,6-trisulphonic acid, 1-hydroxy-8-acetylaminonaphthalene-3sulphonic acid, 1-benzoylamino-8-hydroxynaphthalene-3,6- or -4,6-disulphonic acid, 2-benzoylamino-5-hydroxynaphthalene-7-sulphonic acid, 2-amino-5-hydroxynaphthalene-7-sulphonic acid, 2-methyl- or 2-ethylamino-5-hydroxynaphthalene-7-sulphonic acid, 2-(N-acetyl-N-methylamino)-5-hydroxynaphthalene-7-sulphonic acid, 2-acetylamino-5-hydroxynaphthalene-7-sulphonic acid, 2-amino-5-hydroxynaphthalene-1,7-disulphonic acid, 2-amino-8-hydroxynaphthalene-6-sulphonic acid, 2-methyl- or 2-ethylamino-8-hydroxynaphthalene-6-sulphonic acid, 2-(N-acetyl-N-methylamino)-8-hydroxynaphthalene-6-sulphonic acid, 2-acetylamino-8-hydroxynaphthalene-6-sulphonic acid, 2-amino-8-hydroxynaphthalene-3,6-disulphonic acid, 2-acetylamino-8-hydroxynaphthalene-3,6-disulphonic acid, 1-amino-5-hydroxynaphthalene-7-sulphonic acid, 1-amino-8-hydroxynaphthalene-3,6- or -4,6-disulphonic acid, 1-acetylamino-8-hydroxynaphthalene-3,6- or -4,6-disulphonic acid, 1-(4'-aminobenzoylamino)-8-hydroxynaphthalene-3,6-or -4,6-disulphonic acid, 1-(4'-nitrobenzoylamino)-8-hydroxynaphthalene-3,6- or -4,6-disulphonic acid, 1-(3'-aminobenzoylamino)-8-hydroxynaphthalene-3,6- or -4,6-disulphonic acid, 1-(3'-nitrobenzoylamino)-8-hydroxynaphthalene-3,6- or -4,6-disulphonic acid, 2-(4'-amino-3'-sulphophenylamino)-5-hydroxynaphthalene-7-sulphonic acid, 1-amino-8-hydroxynaphthalene-4-sulphonic acid, 2,4,6-triamino-3-cyanopyridine, 1-β-aminoethyl-3-cyano-4-methyl-6-hydroxypyrid-2-one, 1γ-aminopropyl-3-sulphomethyl-4-methyl-6-hydroxypyrid-2-one and 1,3-diaminobenzene.
The diazotisation of the diazo components or of the intermediate products containing a diazotisable amino group is as a rule carried out by the action of nitrous acid in aqueous-mineral acid solution at a low temperature. The coupling to the coupling components is carried out at strongly acid, neutral to weakly alkaline pH values.
The condensation of the reactive components with the diazo components and the coupling components and with the amines or with acylatable monoazo or disazo intermediate products or with the dyestuffs containing amino groups is preferably carried out in aqueous solution or suspension, at a low temperature and at a weakly acid, neutral to weakly alkaline pH value. The hydrogen halide liberated during the condensation is advantageously neutralised continuously by addition of aqueous alkali metal hydroxides, carbonates or bicarbonates.
The formulae shown are those of the free acids. The salts, in particular the alkali metal salts, such as sodium, potassium or lithium salts, are in general obtained during the preparation. The charge resulting from quaternisation with pyridines is compensated by a counter-ion, for example chloride, fluoride or sulphate, depending on the isolation conditions; or the dyestuffs form inner salts with sulpho or carboxyl groups. The dyestuffs can also be employed as concentrated solutions.
The dyestuffs according to the invention are outstandingly suitable for dyeing and printing naturally occurring and synthetic materials containing OH groups or amide groups, in particular those of cellulose and polyamides. They are particularly suitable for dyeing cellulose materials by the exhaustion and cold pad-batch process, and for printing cotton and viscose staple.
Dyeings having good general fastness properties, in particular wet fastness properties, are obtained, with a good build-up capacity and high fixing yields.
Dyeing Instructions
The dyeings mentioned in the following examples were carried out under the following conditions:
Dyeing instructions 1
2 parts of the dyestuff are dissolved in 100 ml of water. The solution is added to 1900 parts of cold water, 60 parts of sodium chloride are added, and 100 parts of a cotton fabric are introduced into this dyebath.
The temperature is increased to 50° C. 40 parts of calcined sodium carbonate and a further 60 parts of sodium chloride being added after 30 minutes. The temperature is kept at 50° C. for 30 minutes, the fabric is rinsed and the dyeing is then soaped for 15 minutes in a 0.3% strength boiling solution of an ion-free detergent, rinsed and dried.
Dyeing instructions 2
4 parts of the reactive dyestuff are dissolved in 50 parts of water. 50 parts of a solution which contains 5 g of sodium hydroxide and 10 g of calcined sodium carbonate per litre are added. A cotton fabric is padded with the resulting solution such that it increases by 70% of its weight, and is then wound up onto a beam. The cotton fabric is stored thus at room temperature for 3 to 12 hours. The dyed goods are then rinsed, soaped at the boil with a nonionic detergent for a quarter of an hour, rinsed again and dried.
Example 1
a) 0.2 mol of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid is dissolved in 350 ml of water at pH 6.5, and the solution is cooled to 0° C. with 350 g of ice. 0.21 mol of 2,4,6-trifluoro-1,3,5-triazine (cyanuric fluoride) is added, and the pH is kept at between 3.5 and 4 with Na2 CO3 solution. After 5 minutes, 0.2 mol of morpholine is added, and the pH is then brought to 7 with sodium carbonate solution. During this procedure, the temperature rises to about 10° C.
b) 0.2 mol of 3-[4'-(β-chloroethylsulphonyl-methyl)benzoylamino]-aniline-4-sulphonic acid (prepared from 2,4-diaminobenzenesulphonic acid and 4-(β-chloroethylsulphonyl-methyl)-benzoyl chloride) is suspended in water, and 65 ml of 30% strength hydrochloric acid and 300 g of ice are added. 46 ml of 30% strength sodium nitrite solution are then added, and the mixture is stirred at 0° C. for 1 hour. Excess sodium nitrite is destroyed with amido-sulphonic acid, and the diazotisation mixture thus obtained is added to the solution of the coupling component a). A pH of 6-7 is established with sodium carbonate solution.
When the coupling has ended, the dyestuff is salted out, isolated, dried and ground. The dyestuff of the formula ##STR23## thus obtained dyes cotton in clear red shades.
EXAMPLE 2
a) 0.2 mol of 1,4-diaminobenzene-2,5-disulphonic acid is dissolved in 500 ml of water with concentrated sodium hydroxide solution to give a neutral solution The solution is heated to 50° C. and 0.3 mol of 3-(β-chloroethylsulphonyl-methyl)-benzoyl chloride is added. A pH of 7 is maintained by simultaneous addition of sodium carbonate solution (20 g/100 ml). The reaction has ended after 3 hours. The mixture is cooled to 0° C., and 55 ml of 30% strength HCl are added. 47 ml of sodium nitrite solution (30 g/100 ml) are added dropwise at 0° C.-5° C. in the course of 30 minutes. The diazotisation mixture is stirred at 0°-5° C. for 30 minutes. Excess nitrite is then destroyed with amidosulphonic acid.
b) 0.2 mol of 6-amino-l-naphthol-3-sulphonic acid is dissolved in 600 ml of water at pH 7-7.5, with addition of 38 ml of 11% strength lithium hydroxide solution. 0.21 mol of cyanuric fluoride is added dropwise in the course of 30 minutes. During this procedure, a pH of 3.7-4.1 is maintained by simultaneous dropwise addition of 11% strength lithium hydroxide solution. The mixture is subsequently stirred for 5 minutes, and 0.2 mol of morpholine is added. A pH of 7 is established with sodium carbonate solution (20 g/100 ml). The temperature is 5°-8° C. The mixture is subsequently stirred for 15 minutes, and the above diazotisation mixture a) is added dropwise in the course of 1 hour. A pH of 5.5-6.5 is maintained with 1 molar sodium bicarbonate solution. When the coupling has ended, the dyestuff is salted out with NaCl, isolated and dried. The dyestuff of the formula ##STR24## dyes cotton in red shades.
The dyestuffs of the following Examples 3-31 of the general formula ##STR25## can be prepared in an analogous manner using the diazo and coupling components and amines listed. They dye cotton in the colour shades listed.
In the following examples, X represents the following particular radicals: ##STR26##
  Diazo component Coupling component Z Colour shade
  3
  ##STR27##
  ##STR28##
  Red
  4
 ##STR29##
  "
  ##STR30##
  Red
  5
 ##STR31##
  " " Red
  6
 ##STR32##
  "
  ##STR33##
  Red
  7
 ##STR34##
  ##STR35##
  ##STR36##
  Bluish-tinged red
  8
 ##STR37##
  ##STR38##
  " Red
  9
 ##STR39##
  " " Yellowish-tinged red
  10
 ##STR40##
  ##STR41##
  ##STR42##
  Bluish-tinged red
  11
 ##STR43##
  "
  ##STR44##
  Red
  12
 ##STR45##
  "
  ##STR46##
  Red
  13
 ##STR47##
  ##STR48##
  ##STR49##
  Red-violet
  14
 ##STR50##
  "
  ##STR51##
  Red
  15 "
 ##STR52##
  ##STR53##
  Redλ.sub.max = 514 nm,Sh 530 nm
  16
 ##STR54##
  ##STR55##
  ##STR56##
  Red
  17
 ##STR57##
  "
  ##STR58##
  Redλ.sub.max = 512 nm,534 nm
  18
 ##STR59##
  "
  ##STR60##
  Bluish-tinged red
  19
 ##STR61##
  ##STR62##
  ##STR63##
  Red-violet
  20
 ##STR64##
  "
  ##STR65##
  Red
  21
 ##STR66##
  "
  ##STR67##
  Red
   22
 ##STR68##
  ##STR69##
  ##STR70##
  Redλ.sub.max = 514,532 nm
  23
 ##STR71##
  "
  ##STR72##
  Red-violet
  24
 ##STR73##
  " "  Redλ.sub.max = 514,533 nm
  25
 ##STR74##
  ##STR75##
  ##STR76##
  Red
  26
 ##STR77##
  "
  ##STR78##
  Redλ.sub.max 512 nm,535 nm
  27
 ##STR79##
  ##STR80##
  ##STR81##
  Scarlet
  28
 ##STR82##
  ##STR83##
  ##STR84##
  Orange
  29
 ##STR85##
  "
  ##STR86##
  Orange
  30
 ##STR87##
  ##STR88##
  " Scarlet-redλ.sub.max = 506 nm
  31
 ##STR89##
  ##STR90##
  ##STR91##
  Orange
EXAMPLE 32
0.2 mol of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid is dissolved in 450 ml of water at pH 8-9 with sodium hydroxide solution, and 0.22 mol of 2,4,6-trifluoropyrimidine is added. The condensation is carried out at 35°-40° C., the pH being maintained with sodium carbonate solution.
If the product is coupled with the diazotisation mixture described in Example 1, under the same conditions, salting out, isolation and drying give the dyestuff of the formula ##STR92## which dyes cotton in red shades.
EXAMPLE 33
0.2 mol of 8-(4'-amino-benzoylamino)-1-naphthol-3,6-disulphonic acid is dissolved in 800 ml of water at a pH of 7 with sodium carbonate solution (20 g/100 ml). A pH of 4.5 is established with 10% strength CHl solution. 0.2 mol of 2,4,6-trifluoropyrimidine is added, and the mixture is heated up to 30° C. A pH of 4.5-6 is maintained with sodium carbonate solution (20 g/100 ml). The reaction has ended after 4 hours.
0.2 mol of the diazonium salt from Example 1 is now added, and a pH of 7.5-8 is maintained at the same time by dropwise addition of sodium carbonate solution (20 g/100 ml). When the coupling has ended, the dyestuff is salted out with NaCl, isolated and dried. The dyestuff of the formula ##STR93## dyes cotton in red shades.
EXAMPLES 34-68
Examples 34-68 of the formula ##STR94## can be prepared as described in Example 32 or 33 if the corresponding intermediate products are employed. They dye cotton in the colour shades shown. X is represented by X1 to X4 with the abovementioned meanings.
  Diazo component Coupling component Z Colour shade
        34
  ##STR95##
  ##STR96##
  ##STR97##
  Red
  35
 ##STR98##
  ##STR99##
  ##STR100##
  Red-violet
  36
 ##STR101##
  " " Red
  37
 ##STR102##
  " " Bluish-tinged red
  38
 ##STR103##
  ##STR104##
  ##STR105##
  Red
  39
 ##STR106##
  " " Red
  40
 ##STR107##
  " " Bluish-tinged red
  41
 ##STR108##
  ##STR109##
  ##STR110##
  Red
  42
 ##STR111##
  ##STR112##
  " Scarlet
  43
 ##STR113##
  " " Orange
  44
 ##STR114##
  ##STR115##
  ##STR116##
  Red
  45
 ##STR117##
  ##STR118##
  " Orange
  46
 ##STR119##
  ##STR120##
  ##STR121##
  Orange
  47
 ##STR122##
  ##STR123##
  ##STR124##
  Bluish-tinged red
  48
 ##STR125##
  " " Red
  49
 ##STR126##
  "
  ##STR127##
  Red
  50
 ##STR128##
  ##STR129##
  ##STR130##
  Bluish-tinged red
  51
 ##STR131##
  ##STR132##
  " Red
  52
 ##STR133##
  ##STR134##
  " Red
  53
 ##STR135##
  ##STR136##
  ##STR137##
  Red-violet
  54
 ##STR138##
  " " Red
  55
 ##STR139##
  " " Bluish-tinged red
  56
 ##STR140##
  ##STR141##
  ##STR142##
  Red
  57
 ##STR143##
  " " Red
  58
 ##STR144##
  " " Bluish-tinged red
  59
 ##STR145##
  ##STR146##
  ##STR147##
  Red
  60
 ##STR148##
  ##STR149##
  " Scarlet
  61
 ##STR150##
  " " Orange
  62
 ##STR151##
  ##STR152##
  ##STR153##
  Red
  63
 ##STR154##
  ##STR155##
  " Orange
  64
 ##STR156##
  ##STR157##
  ##STR158##
  Bluish-tinged red
  65
 ##STR159##
  " " Red
  66
 ##STR160##
  ##STR161##
  ##STR162##
  Bluish-tinged red
  67
 ##STR163##
  ##STR164##
  " Red
  68
 ##STR165##
  ##STR166##
  " Red
EXAMPLE 69
0.2 mol of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid is dissolved in 650 ml of water at pH 6.5 with sodium hydroxide solution, and the solution is heated to 35° C. 0.21 mol of 2,3-dichloroquinoxaline-6-carbonyl chloride is added to this solution, the pH is brought to 6-7 with sodium carbonate solution and the condensation reaction is carried out at 35° C. for about 6 hours.
Coupling is then carried out with a 3-[4-(β-chloroethylsulphonyl-methyl)-benzoylamino]-aniline-4-sulphonic acid diazotisation mixture analogously to Example 1.
The dyestuff is salted out, isolated, dried and ground. It has the following formula ##STR167## and dyes cotton in red shades.
As described above, the dyestuffs of Examples 70-80 of the formula ##STR168## can be prepared using the diazo and coupling components (K) shown, wherein ##STR169## and X=X1 to X4 has the abovementioned meaning.
__________________________________________________________________________
Ex. Diazo component   K                   Colour shade                    
__________________________________________________________________________
70                                                                        
     ##STR170##                                                           
                       ##STR171##         bluish-tinged red               
71                                                                        
     ##STR172##       "                   red                             
72                                                                        
     ##STR173##       "                   bluish-tinged red               
73                                                                        
     ##STR174##       "                   red                             
74                                                                        
     ##STR175##                                                           
                       ##STR176##         red                             
75                                                                        
     ##STR177##                                                           
                       ##STR178##         bluish-tinged red               
76                                                                        
     ##STR179##                                                           
                       ##STR180##         red-violet                      
77                                                                        
     ##STR181##                                                           
                       ##STR182##         scarlet                         
78                                                                        
     ##STR183##       "                   orange                          
79                                                                        
     ##STR184##       "                   orange                          
80                                                                        
     ##STR185##                                                           
                       ##STR186##         orange                          
__________________________________________________________________________
EXAMPLE 81
0.26 mol of 3-(2-sulphatoethyl)sulphonyl-aniline is dissolved in 250 ml of water with 1 molar sodium bicarbonate solution to give a neutral solution. 250 g of ice are added, and 0.27 mol of cyanuric fluoride is added dropwise. A pH of 4-5 is maintained with 1 molar sodium bicarbonate solution.
The mixture is subsequently stirred for 10 minutes.
0.2 mol of 8-(4'-amino-benzoylamino)-1-naphthol-3,6-disulphonic acid is stirred in 300 ml of water, and dissolved with 11% strength lithium hydroxide solution to give a neutral solution. This solution is added to the above condensation solution. A pH of 6.5-7 is maintained with sodium carbonate solution, and the temperature rises to about 10° C. When the reaction has ended, 0.2 mol of the diazonium salt from Example 1 is added, and a pH of 7.5-8 is maintained at the same time by dropwise addition of sodium carbonate solution (20 g/100 ml). After 3 hours, the dyestuff is salted out with NaCl, isolated and dried. The resulting dyestuff of the formula ##STR187## dyes cotton in red shades.
The dyestuff of Examples 81-90 are obtained analogously using the corresponding diazo components, coupling components and amines. They have the general formula ##STR188## wherein X=X1 to X4 with the abovementioned meaning.
  Ex. Diazo component Coupling component Z Colour shade
  81a
 ##STR189##
  ##STR190##
  ##STR191##
  Scarlet
  82
 ##STR192##
  " " Orange
  83
 ##STR193##
  ##STR194##
  ##STR195##
  Redλ.sub.max =515 nm,SH 535 nm
  84
 ##STR196##
  ##STR197##
  ##STR198##
  Red
  85
 ##STR199##
  " " Red
  86
 ##STR200##
  ##STR201##
  ##STR202##
  Red
  87
 ##STR203##
  ##STR204##
  ##STR205##
  Red
  88
 ##STR206##
  "
  ##STR207##
  Bluish-tinged red
  89
 ##STR208##
  ##STR209##
  " Red
  90
 ##STR210##
  ##STR211##
  ##STR212##
  Red
EXAMPLE 91
a) 0.2 mol of 2-amino-4-(aminomethyl)-benzenesulphonic acid is dissolved in 500 ml of water at a pH of 8 with concentrated sodium hydroxide solution. 0.25 mol of 3-(β-chloroethylsulphonyl-methyl)benzoyl chloride is added. A pH of 7-7.5 is maintained by simultaneous addition of 11% strength lithium hydroxide solution. The temperature is 30° C.-40° C. The mixture is cooled to 0° C. and 56 ml of 30% strength hydrochloric acid are added.
47 ml of sodium nitrite solution (30 g/100 ml) are added dropwise at 0°-5° C. in the course of 1 hour. The diazotisation mixture is subsequently stirred at 0°-5° C. for 1 hour. Excess nitrite is then destroyed by addition of amidosulphonic acid.
b) 0.2 mol of 1-amino-8-hydroxynaphthalene-4,6-disulphonic acid is dissolved in 300 ml of water at pH=5-7 by addition of concentrated sodium hydroxide solution. 300 g of ice are added, and 0.21 mol of cyanuric chloride is sprinkled in. A pH of 4-4.5 is maintained at 0° C. with sodium carbonate solution (20 g/100 ml). When the condensation has ended, 0.2 mol of a neutral solution of 4-chloroaniline in about 200 ml of water is added. The mixture is heated up to 20°-30° C. and the pH is maintained at 6-7 with sodium carbonate solution (20 g/100 ml). After about 1 hour, the mixture is cooled to 10° C., and the above diazotisation mixture a) is added.
At the same time, a pH of 7-7.5 is maintained with sodium carbonate solution (20 g/100 ml).
When the coupling has ended, the dyestuff is salted out with NaCl, isolated and dried. The resulting dyestuff of the formula ##STR213## dyes cotton in red shades.
The dyestuffs of the following Examples 92-111 of the general formula ##STR214## are obtained by varying the diazo components, coupling components and amines. They dye cotton in the shades shown.
X1 and X3 have the abovementioned meaning.
  Ex. Diazo component Coupling component Z Colour shade
  92
 ##STR215##
  ##STR216##
  ##STR217##
  Yellowish-tinged red
  93
 ##STR218##
  ##STR219##
  ##STR220##
  Yellowish-tinged red
  94
 ##STR221##
  ##STR222##
  ##STR223##
  Red
  95
 ##STR224##
  ##STR225##
  ##STR226##
  Yellowish-tinged red
  96
 ##STR227##
  ##STR228##
  ##STR229##
  Red
  97
 ##STR230##
  "
  ##STR231##
  Yellowish-tinged red
  98
 ##STR232##
  ##STR233##
  ##STR234##
  Red
  99
 ##STR235##
  ##STR236##
  " Red
  100
 ##STR237##
  "
  ##STR238##
  Bluish-tinged red
  101
 ##STR239##
  ##STR240##
  ##STR241##
  Red
  102
 ##STR242##
  ##STR243##
  ##STR244##
  Red
  103
 ##STR245##
  "
  ##STR246##
  Red
  104
 ##STR247##
  ##STR248##
  ##STR249##
  Bluish-tinged red
  105
 ##STR250##
  ##STR251##
  ##STR252##
  Red
  106
 ##STR253##
  "
  ##STR254##
  Red
  107
 ##STR255##
  ##STR256##
  ##STR257##
  Scarlet
  108
 ##STR258##
  " " Orange
  109
 ##STR259##
  "
  ##STR260##
  Orange
  110
 ##STR261##
  ##STR262##
  ##STR263##
  Orange
  111
 ##STR264##
  "
  ##STR265##
  Orange
EXAMPLE 112
0.2 mol of 2-aminonaphthalenesulphonic acid is dissolved in 280 ml of water at pH 7 with lithium hydroxide, and 250 g of ice are added. 0.21 mol of cyanuric fluoride is then added, and the pH is kept at about 4 with sodium carbonate solution. A neutral solution of 2,4-diaminobenzenesulphonic acid is added to the suspension thus formed, and the pH is raised to 7-7.5. The reaction temperature is raised to 20° C., and the mixture is stirred for about 1 hour. The reaction mixture is cooled to 0° C., and diazotisation is carried out with HCl and sodium nitrite solution at pH 2-2.2. After the excess nitrite has been destroyed with amidosulphonic acid, the product is coupled to. 1-[4'-(β-chloroethylsulphonyl-methyl)benzoylamino]-8-naphthol-3,6-disulphonic acid, prepared from 4-(β-chloroethylsulphonyl-methyl)-benzoyl chloride and 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid, at pH 5-6 and 10°-15° C. Salting out, isolation and drying give the dyestuff of the formula ##STR266## which dyes cotton in red shades.
The dyestuffs of Examples 113-124 of the general formula ##STR267## where X1 and X3 have the abovementioned meaning, can be prepared in an analogous manner using the diazo and coupling components shown.
In some cases, however, it is more favourable first to synthesise the azo chromophore and then to condense on the reactive components or one of them (Z). They dye cotton in the colour shades shown.
  Ex. Diazo component Coupling component Z Colour shade
        113
  ##STR268##
  ##STR269##
  ##STR270##
  Red-violet
  114
 ##STR271##
  " " Red
  115
 ##STR272##
  "
  ##STR273##
  Bluish-tinged red
  116
 ##STR274##
  ##STR275##
  ##STR276##
  Bluish-tinged red
  117
 ##STR277##
  ##STR278##
  " Red
  118
 ##STR279##
  "
  ##STR280##
  Red
  119
 ##STR281##
  ##STR282##
  ##STR283##
  Red
  120
 ##STR284##
  ##STR285##
  ##STR286##
  Red-violet
  121
 ##STR287##
  "  Red
  122
 ##STR288##
  ##STR289##
  ##STR290##
  Bluish-tinged red
  123
 ##STR291##
  ##STR292##
  " Red
  124
 ##STR293##
  ##STR294##
  ##STR295##
  Red
EXAMPLE 125
0.22 mol of N-ethylaniline is dissolved in 200 ml of water at pH 7. 200 g of ice are added, and 0.24 mol of cyanuric chloride is sprinkled in. A pH of 6-7 is maintained with sodium carbonate solution (20 g/100 ml). The condensation has ended after about 1 hour at 0° C. 0.2 mol of 2,4-diamino-benzenesulphonic acid is dissolved in 250 ml of water by addition of concentrated sodium hydroxide solution, and the solution is added to the first stage of the condensation. A pH of 6-7 is maintained with sodium carbonate solution (20 g/100 ml). The mixture is heated up to 25°-35° C. When the condensation has ended, the mixture is cooled to 0° C. 56 ml of 30% strength hydrochloric acid are added. 47 ml of sodium nitrite solution (30 g/100 ml) are added dropwise, and the mixture is stirred at 0° C. for 1 hour. The sodium nitrite is destroyed with amidosulphonic acid, and the diazotisation mixture thus obtained is added to the coupling component from Example 112. A pH of 7-8 is maintained with sodium carbonate solution (20 g/100 ml). The temperature is 10°-15° C. When the coupling has ended, the dyestuff is salted out with NaCl, isolated and dried. The resulting dyestuff of the formula ##STR296## dyes cotton in red shades.
The dyestuffs of Examples 126-131 of the general formula ##STR297## wherein X=X1 or X3, with the abovementioned meaning, can be prepared analogously, using the corresponding diazo and coupling components and amines. In some cases, it is more advantageous to carry out the condensation with cyanuric chloride and the amine at the end of the synthesis sequence.
  Ex. Diazo component Coupling component Z Colour shade
        126
  ##STR298##
  ##STR299##
  ##STR300##
  Red-violet
  127
 ##STR301##
  "
  ##STR302##
  Bluish-tinged red
  128
 ##STR303##
  "
  ##STR304##
  Bluish-tinged red
  129
 ##STR305##
  ##STR306##
  ##STR307##
  Red
  130
 ##STR308##
  "
  ##STR309##
  Red
  131
 ##STR310##
  ##STR311##
  ##STR312##
  Orange
   EXAMPLE 132
0.2 mol of 6-fluoro-5-chloro-4-(3'-amino-4'-sulphophenyl)-amino-pyrimidine (prepared from 2,4-diaminobenzenesulphonic acid and 4,6-difluoro-5-chloropyrimidine) are suspended in water, and 65 ml of 30% strength hydrochloric acid and 300 g of ice are added. 46 ml of 30% strength sodium nitrite solution are then added, and the mixture is stirred at 0° C. for 1 hour. Excess sodium nitrite is destroyed with amidosulphonic acid, and the diazotisation mixture thus obtained is added to the solution of the coupling component from Example 112. A pH of 7-8 is maintained with sodium carbonate solution (20 g/100 ml). The temperature is 10°-15° C. When the coupling has ended, the dyestuff is salted out with NaCl, isolated and dried. The resulting dyestuff of the formula ##STR313## dyes cotton in red shades.
The dyestuffs of Examples 133-151 of the general formula ##STR314## wherein X=X1 or X3 with the abovementioned meaning, can be prepared analogously, using the corresponding diazo and coupling components and amines.
  Ex. Diazo component Coupling component Z Colour shade
        133
  ##STR315##
  ##STR316##
  ##STR317##
  Red-violet
  134
 ##STR318##
  " " Red
  135
 ##STR319##
  ##STR320##
  " Bluish-tinged red
  136
 ##STR321##
  ##STR322##
  ##STR323##
  Bluish-tinged red
  137
 ##STR324##
  ##STR325##
  " Red
  138
 ##STR326##
  "
  ##STR327##
  Red
  139
 ##STR328##
  ##STR329##
  ##STR330##
  Red
  140
 ##STR331##
  ##STR332##
  " Red-violet
  141
 ##STR333##
  " " Red
  142
 ##STR334##
  ##STR335##
  ##STR336##
  Bluish-tinged red
  143
 ##STR337##
  ##STR338##
  " Red
  144
 ##STR339##
  ##STR340##
  " Red
  146
 ##STR341##
  ##STR342##
  ##STR343##
  Red-violetλ.sub.max = 514 nm,535 nm
  147
 ##STR344##
  " " Bluish-tinged red
  148
 ##STR345##
  ##STR346##
  ##STR347##
  Bluish-tinged red
  149
 ##STR348##
  ##STR349##
  ##STR350##
  Red
  150
 ##STR351##
  ##STR352##
  ##STR353##
  Red
  151
 ##STR354##
  ##STR355##
  ##STR356##
  Orange
Other useful dyestuffs of the formulae ##STR357## are those in Examples 152-163, which can be prepared by known methods, as described, for example, above, and dye cotton in the shades shown.
       Colour Ex. X Diazo component K Z shade
         152
  ##STR358##
  ##STR359##
  ##STR360##
  ##STR361##
  Goldenyellow
  153
 ##STR362##
  ##STR363##
  ##STR364##
  ##STR365##
  Goldenyellow
  154 "
 ##STR366##
  ##STR367##
  ##STR368##
  Reddish-tingedyellow
  155
 ##STR369##
  ##STR370##
  ##STR371##
  ##STR372##
  Reddish-tingedyellow
  156 " "
 ##STR373##
  ##STR374##
  Bluish-tingedred
  157
 ##STR375##
  ##STR376##
  ##STR377##
  ##STR378##
  158
 ##STR379##
  ##STR380##
  ##STR381##
  ##STR382##
  Violet
  159 " "
 ##STR383##
  " Yellow
  160 "
 ##STR384##
  ##STR385##
  " Goldenyellow
  161
 ##STR386##
  ##STR387##
  ##STR388##
  ##STR389##
  Goldenyellow
  162
 ##STR390##
  ##STR391##
  ##STR392##
  ##STR393##
  Goldenyellow
  163
 ##STR394##
  ##STR395##
  ##STR396##
  ##STR397##
  Goldenyellow
The dyestuffs of Examples 164-189 can be obtained analogously to the preparation processes described above, or by customary processes, using the corresponding starting components. ##STR398##

Claims (11)

We claim:
1. A reactive dyestuff of the formula
where X= ##STR399## FB=the radical of a dyestuff, B and B1 =identically or differently, a direct bond or a bridge member to a ring C atom of an aromatic-carbocyclic or to a ring C or N atom of an aromatic-heterocyclic ring in FB,
M=CH═CH2 or CH2 CH2 --V, wherein
V=OH or a radical which can be eliminated under alkaline conditions,
Z=a heterocyclic fibre-reactive radical without a further chromophoric part and
R and R1 =independently of one another, H or substituted or unsubstituted C1 -C6 -alkyl.
2. A dyestuff of claim 1, in which FB is a mono- or polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan, azomethine, dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthone, nitroaryl, naphthoquinone, pyrene-quinone or perylenetetracarbimide radical.
3. Dyestuff of claim 1, wherein B and B1 are a single bond and ##STR400##
4. Dyestuff of claim 1, of the formula ##STR401## wherein -X represents ##STR402## and D, D1 and D2 =independently of one another, the radical of a diazo component of the benzene or naphthalene series and
K=the radical of a coupling component of the benzene, naphthalene, acetoacetic acid arylide or heterocyclic series, and in the formulae (1d) and (1e)=the radical of a coupling component with two coupling sites,
and wherein
M, B and B1 have the meaning given in claim 1.
5. Dyestuff of claim 1, where
Z=a fibre-reactive fluorine-containing 4-pyrimidyl radical,
or where Z= ##STR403## wherein R4 and R5 independently of one another denote hydrogen, C1-4 -alkyl, which is unsubstituted or substituted by halogen, cyano, C1-4 -alkoxy, hydroxyl, carboxyl, sulpho or sulphato, benzyl, phenethyl, cyclohexyl, phenyl or --NHCH2 CH2 OCH2 CH2 --SO2 M, wherein M has the meaning given in claim 1, phenyl, which is optionally substituted by halogen, nitro, cyano, trifluoromethyl, sulphamoyl, carbamoyl, C1-4 -alkyl, C1-4 -alkoxy, C1-4 -alkanoylamino, benzoylamino, ureido, hydroxyl, carboxyl, sulphomethyl or sulpho, or naphthyl, which is optionally substituted by halogen, nitro, C1-4 -alkoxy, C1-4 -alkanoylamino, hydroxyl, carboxyl or sulpho,
or wherein R4 and R5, together with the amino nitrogen atom, form a morpholino, piperidino or piperazino radical, and wherein
Y is Cl, F or an unsubstituted or substituted pyridinium radical.
6. Dyestuff according to claim 1, characterised in that
M=CH═CH2 or CH2 CH2 Cl.
7. Dyestuff according to claim 1, wherein Z represents ##STR404## wherein Y=Cl, F or an unsubstituted or substituted pyridinium radical,
M=CH═CH2 or CH2 CH2 --V, wherein
V=a radical which can be eliminated under alkaline conditions,
R10 =H or unsubstituted or substituted C1 -C6 -alkyl and
R2 =H, Cl, Br, C1 -C4 -alkyl, C1 -C4 -alkoxy, CO2 H or SO3 H.
8. Dyestuff of claim 1, of the formulae ##STR405## wherein Pc represents a Cu or Ni phthalocyanine radical and the total number of substituents on the Pc skeleton is not more than 4, ##STR406## wherein T=Cl, Br or OCH3,
R and R3 =H, CH3 or C2 H5,
R6 =H, C1 -C4 -alkyl, C1 -C4 -alkoxy, acylamino, C1 -C4 -alkylsulphonylamino, aminocarbonylamino, phenylcarbonylamino, Cl or Br,
R7 =H, C1 -C4 -alkyl, C1 -C4 -alkoxy, OH or SO3 H,
K=the radical of a coupling component of the benzene, naphthalene, acetoacetic acid anilide or heterocyclic series,
M=CH═CH2 or CH2 CH2 Cl,
Z represents ##STR407## wherein R4 and R5 independently of one another denote hydrogen, C1-4 -alkyl, which is unsubstituted or substituted by halogen, cyano, C1-4 -alkoxy, hydroxyl, carboxyl, sulpho or sulphato, benzyl, phenethyl, cyclohexyl, phenyl or --NHCH2 CH2 OCH2 CH2 --SO2 M, phenyl, which is optionally substituted by halogen, nitro, cyano, trifluoromethyl, sulphamoyl, carbamoyl, C1-4 -alkyl, C1-4 -alkoxy, C1-4 -alkanoylamino, benzoylamino, ureido, hydroxyl, carboxyl, sulphomethyl or sulpho, or naphthyl, which is optionally substituted by halogen, nitro C1-4 -alkoxy, C1-4 -alkanoylamino, hydroxyl, carboxyl or sulpho, or
wherein
R4 and R5, together with the amino nitrogen atom, form a morpholino, piperidino or piperazino radical, and
wherein
Y is Cl, F or an unsubstituted or substituted pyridinium radical, or
Z represents ##STR408## wherein Y has the aforesaid meaning,
R10 =H or unsubstituted or substituted C1 -C6 -alkyl, and
R2 =H, Cl, Br, C1 -C4 -alkyl, C1 -C4 -alkoxy, CO2 H or SO3 H,
W=an aliphatic bridge member and
Alk=straight-chain or branched C1 -C6 -alkylene which is optionally interrupted by hetero atoms or groupings containing hetero atoms selected from the group consisting of NR, O and S, wherein
the benzene rings E are substituted by CH3, C2 H5 --, CH3 O, C2 H5 O, halogen, CO2 H or unsubstituted.
9. Dyestuff of claim 1 of the formula ##STR409## wherein R4 and R5 independently of one another are hydrogen, C1-4 -alkyl, which is unsubstituted or substituted by halogen, cyano, C1-4 -alkoxy, hydroxyl, carboxyl, sulpho or sulphato, benzyl, phenethyl, cyclohexyl, phenyl or --NHCH2 CH2 OCH2 CH2 --SO2 M (M=--CH═CH2 or --CH2 CH2 V, where V=a radical which can be eliminated under alkaline conditions), phenyl, which is unsubstituted or substituted by halogen, nitro, cyano, trifluoromethyl, sulphamoyl, carbamoyl, C1-4 -alkyl, C1-4 -alkoxy, C1-4 -alkanoylamino, benzoylamino, ureido, hydroxyl, carboxyl, sulphomethyl or sulpho, or naphthyl, which is optionally substituted by halogen, nitro, C1-4 -alkoxy, C1-4 -alkanoylamaino, hydroxyl, carboxyl or sulpho,
or wherein R4 and R5, together with the amino nitrogen atom, form a morpholino, piperidino or piperazino radical, and R represents H, CH3 or C2 H5.
10. Dyestuff of claim 1 of the formula ##STR410## wherein Z=a fibre-reactive halogen-containing pyrimidinyl radical and
R=H, CH3 or C2 H5.
11. Process for dyeing and printing materials containing hydroxyl groups and materials containing amide groups, by applying thereto a dyestuff of claim 1.
US08/004,807 1992-01-22 1993-01-15 Reactive dyestuffs for dyeing and printing materials containing OH groups or amide groups Expired - Fee Related US5378817A (en)

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